MACROCYCLE COMPLEXATION CHEMISTRY .37. THE ISOLATION AND CRYSTALLOGRAPHIC CHARACTERIZATION OF THE U4+ AND UO-2(2+) EXTRACTION COMPLEXES [(H5O2)(DICYCLOHEXANO-24-CROWN-8)]2 [UO2CL4].MEOH AND [(H5O2) (DICYCLOHEXANO-24-CROWN-8)]2 [UCL6].MEOH

被引:12
作者
ROGERS, RD
BENNING, MM
机构
[1] Department of Chemistry, Northern Illinois University, DeKalb, 60115, IL
来源
JOURNAL OF INCLUSION PHENOMENA AND MOLECULAR RECOGNITION IN CHEMISTRY | 1991年 / 11卷 / 02期
关键词
DICYCLOHEXANO-24-CROWN-8; HYDRONIUM URANYL CHLORIDE METHANOL SOLVATE COMPLEX; HYDRONIUM URANIUM(IV) CHLORIDE METHANOL SOLVATE COMPLEX; X-RAY CRYSTAL STRUCTURE;
D O I
10.1007/BF01153296
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The reaction of dicyclohexano-24-crown-8 with UCl4 in 3/1 THF:MeOH under anhydrous conditions and with exposure to air, resulted in the isolation of the hydronium ion complexes, [(H5O2)(dicyclohexano-24-crown-8)]2[UO2Cl4].MeOH and [(H5O2)(dicyclohexano-24-crown-8)]2[UCl6].MeOH. The [UO2Cl4]2- complex crystallizes in the monoclinic space group, P2(1)/n, with a = 15.200(8), b = 26.565(9), c = 16.977(8) angstrom, beta = 95.89(6)-degrees and D(calc) = 1.40 g cm-3 for Z = 4 formula units. A final R value of 0.051 was obtained utilizing 5913 independent observed [F(o) greater-than-or-equal-to 5-sigma(F(o))] reflections. One ether is complexed by an ordered H5O2+ ion, while the second crown ether is hydrogen bonded to a disordered H5O2+ ion. The [UCl6]2- complex is tetragonal, P4/n, with (at -150-degrees-C) a = 16.320(4), c = 12.542(2) angstrom and D(calc) = 1.47 g cm-3 for Z = 2. A final R value of 0.038 was obtained utilizing 2466 observed reflections. The anion resides on a four-fold axis and the crown ether cation around a crystallographic two-fold axis. The H5O2+ ion is disordered into two orientations within the macrocycle cavity. All three crystallographically independent crown ether environments in these two structures have essentially identical conformations.
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页码:121 / 135
页数:15
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